TWI414527B - Isosorbide derivatives and liquid crystal displays comprising the same - Google Patents

Abstract

An isosorbide derivative of Formula (I) is provided. In Formula (I), Z is —CH2—CH2—, —CH═CH—, —C≡C—, —CH2—O—, —CH2—S—, —CH═N—O—, —CO—O—, —CO—S—, single bond, -ph-, —CO—O-ph- or —CO—O-ph-CO—O—, and ph represents benzene, R1 and R2 are, independently, C1-25 alkyl, —CN, —NCS, —CX3 or —OCX3, and X represents halogen, and m and n are, independently, 0, 1 or 2. The invention also provides a liquid crystal display including the isosorbide derivative.

Description

Isosorbide derivative and liquid crystal display comprising the same

This invention relates to an isosorbide derivative, and more particularly to an isosorbide derivative doped on a liquid crystal display.

In recent years, due to the development of the liquid crystal industry, liquid crystal materials have been developed for various needs. Among them, cholesteric liquid crystals have bistability and can be maintained without external voltage. The performance of the picture, therefore, has the opportunity to become a new generation of flat display technology.

The cholesteric liquid crystal material has both a spiral structure and a liquid crystal property. The helical structure is usually formed by doping a chiral dopant into a cholesteric liquid crystal molecule without palmarity. Therefore, the helical twisting power (HTP) of the palm molecular is the main factor determining the degree of helical twist of the cholesteric liquid crystal. In general, each pair has a different HTP for its palm structure.

A chiral dopant is an optically active substance. When a palmitic dopant is added to a liquid crystal having a nematic phase, the liquid crystal is rotated into a cholesteric liquid crystal phase. The size of the helical torsion (HTP) of the palmitic molecule is mainly determined by the characteristics of the palmitic dopant itself, but also by the influence of the nematic liquid crystal host and temperature.

An embodiment of the present invention provides an isosorbide derivative having the following chemical formula (I):

Wherein Z is -CH ₂ -CH ₂ -, -CH=CH-, -C≡C-, -CH ₂ -O-, -CH ₂ -S-, -CH=NO-, -CO-O-, - CO-S-, single bond, -ph-, -CO-O-ph- or -CO-O-ph-CO-O-, wherein ph is phenyl; R ₁ and R _{2 are} independently carbon number 1~ 25 alkyl, -CN, -NCS, -CX ₃ or -OCX ₃ wherein X is halogen; and m and n are independently 0, 1 or 2.

An embodiment of the present invention provides a liquid crystal display comprising: an upper substrate; a lower substrate disposed opposite the upper substrate; and a liquid crystal layer disposed between the upper substrate and the lower substrate, including an isosorbide An isosorbide derivative having the following chemical formula (I):

Wherein Z is -CH ₂ -CH ₂ -, -CH=CH-, -C≡C-, -CH ₂ -O-, -CH ₂ -S-, -CH=NO-, -CO-O-, - CO-S-, single bond, -ph-, -CO-O-ph- or -CO-O-ph-CO-O-, wherein ph is phenyl, R ₁ and R _{2 are} independently carbon number 1~ 25 alkyl, -CN, -NCS, -CX ₃ or -OCX ₃ wherein X is halogen and m and n are independently 0, 1 or 2.

The present invention develops a novel isosorbide derivative to a chiral dopant whose core structure is composed of isosorbide and which is made of piperazine. Side chain structure. The isosorbide derivative of the present invention has been tested and proved to be effective for improving the temperature stability of, for example, cholesteric liquid crystal (for example, its temperature dependence is less than or equal to 0.2 nm/°C). In addition, the isosorbide derivative also has a large helical twisting power (HTP) (for example, may be greater than 45 μm ^-1 ), which is quite helpful for increasing the degree of helical twist of the cholesteric liquid crystal.

The above described objects, features and advantages of the present invention will become more apparent and understood.

An embodiment of the present invention provides an isosorbide derivative having the following chemical formula (I):

In the formula (I), Z may be -CH ₂ -CH ₂ -, -CH=CH-, -C≡C-, -CH ₂ -O-, -CH ₂ -S-, -CH=NO-, -CO-O-, -CO-S-, single bond, -ph-, -CO-O-ph- or -CO-O-ph-CO-O-, the above ph represents a phenyl group.

R ₁ and R ₂ may independently be an alkyl group having 1 to 25 carbon atoms, -CN, -NCS, -CX ₃ or -OCX ₃ , and X represents a halogen.

m and n may independently be 0, 1, or 2.

Specific examples of the isosorbide derivatives of the present invention are listed below:

An embodiment of the present invention provides a liquid crystal display including an upper substrate, a lower substrate disposed opposite the upper substrate, and a liquid crystal layer disposed between the upper substrate and the lower substrate, including an isosorbide a derivative having the following chemical formula (I):

In the formula (I), Z may be -CH ₂ -CH ₂ -, -CH=CH-, -C≡C-, -CH ₂ -O-, -CH ₂ -S-, -CH=NO-, -CO-O-, -CO-S-, single bond, -ph-, -CO-O-ph- or -CO-O-ph-CO-O-, the above ph represents a phenyl group.

R ₁ and R ₂ may independently be an alkyl group having 1 to 25 carbon atoms, -CN, -NCS, -CX ₃ or -OCX ₃ , and X represents a halogen.

m and n may independently be 0, 1, or 2.

The isosorbide derivative of the present invention can be doped to a liquid crystal display such as cholesteric liquid crystal.

The present invention develops a novel isosorbide derivative to a chiral dopant whose core structure is composed of isosorbide and which is made of piperazine. Side chain structure. The isosorbide derivative of the present invention has been tested and proved to be effective for improving the temperature stability of, for example, cholesteric liquid crystal (for example, its temperature dependence is less than or equal to 0.2 nm/°C). In addition, the isosorbide derivative also has a large helical twisting power (HTP) (for example, may be greater than 45 μm ^-1 ), which is quite helpful for increasing the degree of helical twist of the cholesteric liquid crystal.

[Examples]

[Example 1]

Synthesis of isosorbide derivatives of the invention 1

First, 2.2 g of 4-[4-methyl-piperazin-1-yl]-benzoic acid (10 mmol) and 2.43 g of 1 , 1"-Carbonyldiimidazole (CDI) (15 mmol) was placed in a 100 mL double neck round bottom bottle. Thereafter, under a nitrogen (N ₂ ) atmosphere, 30 ml of anhydrous tetrahydrofuran (THF) was charged. After heating to reflux for four hours, it was allowed to stand at room temperature to complete the preparation of the A solution.

Next, 0.45 g of Isosorbide (3 mmol) was placed in another round bottom flask and dissolved in tetrahydrofuran (THF) under ice bath. Thereafter, sodium hydride (NaH) was added to complete the preparation of the B solution. After two hours, the above A solution was poured into the B solution and stirred to room temperature for about two hours. After drying, a yellow solid was obtained. Then, by recrystallization using methanol (MeOH), 1.15 g of Compound A-2C1 was obtained in a yield of 70%.

[Example 2]

Synthesis of isosorbide derivatives of the invention 2

First, 2.76 g of 4-[4-Pentyl-piperazin-1-yl]-benzoic acid (10 mmol) and 2.43 g of 1 , 1"-Carbonyldiimidazole (CDI) (15 mmol) was placed in a 100 mL double neck round bottom bottle. Thereafter, under a nitrogen (N ₂ ) atmosphere, 30 ml of anhydrous tetrahydrofuran (THF) was charged. After heating to reflux for four hours, it was allowed to stand at room temperature to complete the preparation of the A solution.

Next, 0.45 g of Isosorbide (3 mmol) was placed in another round bottom flask and dissolved in tetrahydrofuran (THF) under ice bath. Thereafter, sodium hydride (NaH) was added to complete the preparation of the B solution. After two hours, the above A solution was poured into the B solution and stirred to room temperature for about two hours. After drying, a yellow solid was obtained. Subsequently, by recrystallization using methanol (MeOH), 1.25 g of Compound A-2C5 was obtained in a yield of 63%.

[Example 3]

Synthesis of isosorbide derivatives of the invention 3

First, 2.76 g of 4-[4-(1-methyl-butyl)-piperazin-1-yl]-benzoic acid (4-[4-(1-Methyl-butyl)-piperazin-1-yl) ]-benzoic acid) (10 mmol) and 2.43 g of 1,1"-carbonyldiimidazole (CDI) (15 mmol) were placed in a 100 ml double neck round bottom flask. Thereafter, under a nitrogen (N ₂ ) atmosphere, 30 ml of anhydrous tetrahydrofuran (THF) was charged. After heating to reflux for four hours, it was allowed to stand at room temperature to complete the preparation of the A solution.

Next, 0.45 g of Isosorbide (3 mmol) was placed in another round bottom flask and dissolved in tetrahydrofuran (THF) under ice bath. Thereafter, sodium hydride (NaH) was added to complete the preparation of the B solution. After two hours, the above A solution was poured into the B solution and stirred to room temperature for about two hours. After drying, a yellow solid was obtained. Then, by recrystallization using methanol (MeOH), 1.29 g of Compound A-2IC5 was obtained in a yield of 65%.

[Embodiment 4]

Synthesis of isosorbide derivatives of the invention 4

First, 3.52 g of 4-[4-(4-pentyl-phenyl)-piperazin-1-yl]-benzoic acid (4-[4-(4-Pentyl-phenyl)-piperazin-l-yl) ]-benzoic acid) (10 mmol) and 2.43 g of 1,1"-carbonyldiimidazole (CDI) (15 mmol) were placed in a 100 ml double neck round bottom flask. Thereafter, under a nitrogen (N ₂ ) atmosphere, 30 ml of anhydrous tetrahydrofuran (THF) was charged. After heating to reflux for four hours, it was allowed to stand at room temperature to complete the preparation of the A solution.

Next, 0.45 g of Isosorbide (3 mmol) was placed in another round bottom flask and dissolved in tetrahydrofuran (THF) under ice bath. Thereafter, sodium hydride (NaH) was added to complete the preparation of the B solution. After two hours, the above A solution was poured into the B solution and stirred to room temperature for about two hours. After drying, a yellow solid was obtained. Subsequently, by recrystallization using methanol (MeOH), 1.61 g of Compound A-2BC5 was obtained in a yield of 66%.

[Embodiment 5]

Synthesis of isosorbide derivatives of the invention 5

First, 2.2 g of 4-[4-methyl-piperazin-1-yl]-benzoic acid (10 mmol) and 2.43 g of 1 , 1"-Carbonyldiimidazole (CDI) (15 mmol) was placed in a 100 mL double neck round bottom bottle. Thereafter, under a nitrogen (N ₂ ) atmosphere, 30 ml of anhydrous tetrahydrofuran (THF) was charged. After heating to reflux for four hours, it was allowed to stand at room temperature to complete the preparation of the A solution.

Next, 1.9 g of Isosorbide (13 mmol) was placed in another round bottom flask and dissolved in tetrahydrofuran (THF) under ice bath. Thereafter, sodium hydride (NaH) was added to complete the preparation of the B solution. After two hours, the above A solution was poured into the B solution and stirred to room temperature for about two hours. After drying, a yellow solid was obtained. Next, column chromatography (with EA:HEX = 1:1 as a water-filled liquid) was carried out to obtain 2.1 g of an intermediate (6 mmol) in a yield of 66%.

Thereafter, 2.21 g of 4-[4-Pentyl-piperazin-1-yl]-benzoic acid (8 mmol) and 2.43 g of 1 , 1"-Carbonyldiimidazole (CDI) (15 mmol) was placed in a 100 mL double neck round bottom bottle. Thereafter, under a nitrogen (N ₂ ) atmosphere, 30 ml of anhydrous tetrahydrofuran (THF) was charged. After heating to reflux for four hours, it was allowed to stand at room temperature to complete the preparation of the C solution.

Next, the above intermediate was placed in another round bottom flask and dissolved in tetrahydrofuran (THF) under ice bath. Thereafter, sodium hydride (NaH) was added to complete the preparation of the D solution. After two hours, the above C solution was poured into the D solution and stirred to room temperature for about two hours. After drying, a yellow solid was obtained. Subsequently, by recrystallization using methanol (MeOH), 1.83 g of Compound A-C1C5 was obtained in a yield of 50%.

[Embodiment 6]

Synthesis of isosorbide derivatives of the invention 6

First, 3.40 g of 4-(4-carboxy-phenyl)-piperazine-1-carboxylic acid-p-tolyl (4-(4-Carboxy-phenyl)-piperazin-1-carboxylic acid-p- Tolyl ester) (10 mmol) and 2.43 g of 1,1"-carbonyldiimidazole (CDI) (15 mmol) were placed in a 100 mL double neck round bottom flask. Thereafter, under a nitrogen (N ₂ ) atmosphere, 30 ml of anhydrous tetrahydrofuran (THF) was charged. After heating to reflux for four hours, it was allowed to stand at room temperature to complete the preparation of the A solution.

Next, 0.45 g of Isosorbide (3 mmol) was placed in another round bottom flask and dissolved in tetrahydrofuran (THF) under ice bath. Thereafter, sodium hydride (NaH) was added to complete the preparation of the B solution. After two hours, the above A solution was poured into the B solution and stirred to room temperature for about two hours. After drying, a yellow solid was obtained. Then, by recrystallization using methanol (MeOH), 1.54 g of Compound A-2aBC1 was obtained in a yield of 65%.

[Embodiment 7]

Synthesis of isosorbide derivatives of the invention 7

First, 2.31 g of 4-(4-cyano-piperazin-1-yl)-benzoic acid (10 mmol) and 2.43 g of 1 , 1"-Carbonyldiimidazole (CDI) (15 mmol) was placed in a 100 mL double neck round bottom bottle. Thereafter, under a nitrogen (N ₂ ) atmosphere, 30 ml of anhydrous tetrahydrofuran (THF) was charged. After heating to reflux for four hours, it was allowed to stand at room temperature to complete the preparation of the A solution.

Next, 0.45 g of Isosorbide (3 mmol) was placed in another round bottom flask and dissolved in tetrahydrofuran (THF) under ice bath. Thereafter, sodium hydride (NaH) was added to complete the preparation of the B solution. After two hours, the above A solution was poured into the B solution and stirred to room temperature for about two hours. After drying, a yellow solid was obtained. Subsequently, recrystallization was carried out using methanol (MeOH) to give 0.9 g of Compound A-2CN in a yield of 68%.

[Embodiment 8]

Synthesis of isosorbide derivatives of the invention 8

First, 2.74 g of 4-(4-Trifluoromethyl-piperaZin-l-yl)-benzoic acid (10 mmol) and 2.43 g. 1,1"-Carbonyldiimidazole (CDI) (15 mmol) was placed in a 100 mL two-necked round bottom flask. Thereafter, under a nitrogen (N ₂ ) atmosphere, 30 ml of anhydrous tetrahydrofuran (THF) was charged. After heating to reflux for four hours, it was allowed to stand at room temperature to complete the preparation of the A solution.

Next, 0.45 g of Isosorbide (3 mmol) was placed in another round bottom flask and dissolved in tetrahydrofuran (THF) under ice bath. Thereafter, sodium hydride (NaH) was added to complete the preparation of the B solution. After two hours, the above A solution was poured into the B solution and stirred to room temperature for about two hours. After drying, a yellow solid was obtained. Then, by recrystallization using methanol (MeOH), 1.18 g of Compound A-2CF3 was obtained in a yield of 60%.

[Embodiment 9]

Helix Torsional Force (HTP) and Temperature Dependence of Isosorbide Derivatives of the Invention

The physicochemical properties of the isosorbide derivatives (compounds A-2C1, A-2C5, A-2IC5, A-2BC5, A-C1C5, A-2aBC1, A-2CN, A-2CF3) of the present invention, For example, helical twisting power (HTP) and temperature dependence (dλ/dT) are shown in Table 1 below. The measurement temperature is 20~50 °C.

As can be seen from Table 1, the isosorbide derivatives of the present invention (compounds A-2C1, A-2C5, A-2IC5, A-2BC5, A-C1C5, A-2aBC1, A-2CN, A- 2CF3) has a large helical twisting force (HTP), for example, both are larger than 45 μm ^-1 , and its temperature dependency is low, for example, both are less than or equal to 0.2 nm / ° C, and therefore, it is quite suitable for use in a liquid crystal display such as cholesteric liquid crystal.

While the present invention has been described in its preferred embodiments, the present invention is not intended to limit the invention, and the invention may be modified and retouched without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application attached.

Claims (4)

An isosorbide derivative having the following chemical formula (I): Wherein Z is -CH ₂ -CH ₂ -, -CH=CH-, -C≡C-, -CH ₂ -O-, -CH ₂ -S-, -CH=NO-, -CO-O-, - CO-S-, single bond, -ph-, -CO-O-ph- or -CO-O-ph-CO-O-, wherein ph is phenyl; R ₁ and R _{2 are} independently carbon number 1~ 25 alkyl, -CN, -NCS, -CX ₃ or -OCX ₃ wherein X is halogen; and m and n are independently 0, 1 or 2. The isosorbide derivative according to claim 1, wherein the isosorbide derivative comprises: or A liquid crystal display comprising: an upper substrate; a lower substrate disposed opposite to the upper substrate; and a liquid crystal layer disposed between the upper substrate and the lower substrate, comprising an isosorbide derivative having The following chemical formula (I): Wherein Z is -CH ₂ -CH ₂ -, -CH=CH-, -C≡C-, -CH ₂ -O-, -CH ₂ -S-, -CH=NO-, -CO-O-, - CO-S-, single bond, -ph-, -CO-O-ph- or -CO-O-ph-CO-O-, wherein ph is phenyl, R ₁ and R _{2 are} independently carbon number 1~ 25 alkyl, -CN, -NCS, -CX ₃ or -OCX ₃ wherein X is halogen and m and n are independently 0, 1 or 2. The liquid crystal display of claim 3, wherein the liquid crystal display is a cholesteric liquid crystal display.